Catalysts are Essentially made up of Two Part

(Active component & Carrier)

Most common catalysts used in the industry are metals and

metal oxides, such as:
Pt, Pd, Rh, Ni, Co, Fe, V
2
O
5
, MoO

, Cr
2
O

, etc!

"hese acti#e com$onents are then dis$ersed on a carrier

%su$$ort& such as 'l
2
O

, (iO
2
, "iO
2
, )eolites, crystalline
alumina*silicates, etc!

Carriers are hi+h sur,ace area inor+anic material containin+ a

com$lex $ore structure on -hich the acti#e com$onent is
dis$ersed

Carrier or su$$ort -as thou+ht to $ro#ide a hi+her dis$ersion

o, the acti#e com$onent to maximi)e the catalytic sur,ace area
Recently, it has .een sho-n to also $lay a critical role in controllin+ the
acti#ity, selecti#ity and dura.ility o, the ,inished catalysts
Commonly used carriers in the industry are
Al
2
O
3
!iO
2
TiO
2
and "eolites
Al
2
O
3

it is o, di,,erent ty$es $ossessin+ #aryin+ sur,ace areas, $ore

si)e distri.ution, sur,ace acidic $ro$erties and crystal structure
these $ro$erties de$end on its $re$aration, $urity and thermal history
"he initial 'l
2
O

is $roduced .y $reci$itation %$$t& either ,rom

acidic or .asic solutions -hich results in di,,erent ty$es o,
alumina
.ayerite %'l
2
O

!/
2
O& is ,ormed -hen $$t ,rom a solution at $/ 00
$seudo*.oehmite %'l
2
O

!/
2
O& is ,ormed -hen $$t ,rom a solution at $/
1
acidic $/ %$/ 23& the alumina ,ormed is amor$hous %no lon+ ran+e
order&
'l
2
O

contd

Once $reci$itated it is thorou+hly -ashed to remo#e

im$urities

i, acidic solutions are neutrali)ed -ith NaO/, the Na

4
ions
are remo#ed .y -ashin+

Follo-in+ $$t and -ashin+ the alumina is dried at 005

o
C to
remo#e excess -ater and other #olatile s$ecies %N/

&

Calcination at 2555
o
C ,orms the ,inal sur,ace area su$$ort

calcinations at di,,erent tem$eratures determines the ,inal

crystal structure 67 determines $hysical and chemical
$ro$erties
8i,,erent crystal $hases o, 'l
2
O

are ,ormed
de$endin+ on treatment
555*955 955*0555 0555*0055 7 0055
:oehmite +amma delta theta al$ha
%monohydrate& %;& %<& %=& %>&

55*555 955*0555 70055
:ayerite eta theta al$ha
%trihydrate& %?& %=& %>&

Chan+es are irre#ersi.le -ith a loss o, sur,ace area and other $ro$erties %e!+!, O/, acidity&
Colla$se o, sur,ace area may also occlude the acti#e sites -ithin its $ore structure resultin+ in a loss o,
accessi.ility %catalyst deacti#ation&
Presence o, certain element%s& has an in,luence on the sur,ace area chan+es at hi+h tem$eratures
e!!+!, small amounts o, Na
2
O enhances sinterin+
small amounts o, @a
2
O, CeO
2
, :aO and (iO
2
sta.ili)e the sur,ace area reduces the mo.ility
o, the 'l and O ions
(iO
2
As$ecially use,ul to-ards sul,ur .earin+ com$ounds %'l
2
O

is #ery
reacti#e 67 deacti#ation&
'lBaline solutions o, silicate %$/ 702& are neutrali)ed -ith acid
resultin+ in the ,ormation o, silicic acid
silicic acid $olymeri)es ,ormin+ a hi+h sur,ace area net-orB -ith
interconnectin+ $ores o, #aryin+ si)es

/
4
(iO
2
*2
C(i%O/&
D
E
x
(iO
2
!/
2
O
(imilar to 'l
2
O

it is -ashed, dried and calcined

sur,ace areas in the ran+e o, 55 355 m
2
F+
"iO
2

Assentially t-o ty$es o, crystal structures exist, anatase and

rutile

anatase is the more im$ortant ,orm due to its hi+her

sur,ace area and is thermally sta.le u$ to 555
o
C

rutile structure has a lo- sur,ace area %G 05 m

2
F+& and is
,ormed at 2 555
o
C

8ue to the relati#ely lo- tem$eratures reHuired ,or

con#ersion o, anatase and rutile care must .e taBen
other-ise occlusion o, acti#e sites can occur
'natase "iO
2
is $re$ared .y $reci$itation ,rom titanate
solutions or .y decom$osition o, or+anic titanates

this is ,ollo-ed .y -ashin+, dryin+ and mild calcinations

Ieolites are a class o, alumina*
silicates

Jith -ell*de,ined crystalline structures and $ore si)e

naturally occurrin+ or synthetic

the 'l
2
O

and (iO
2
are .ound to+ether as D co*ordinated
units

each 'l and (i cation is .onded to ,our oxy+en

each O
*2
is .onded to either (i
4D
or 'l
4

CFi+ureE

'n extra Na
4
or /
4
must .e $resent ,or char+e neutrality

this extra cation +i#es rise to an exchan+ea.le cation

site

-hen /
4
is $resent the sites are acidic

Pore structures can .e maintained .et-een and 9 '

o
,
-hich is the ran+e o, small reactant molecules

lar+er molecules are $re#ented ,rom enterin+ the )eolite

%molecular sie#es&
Axam$le o, a )eolite is mordenite
%synthetic )eolite&
Na
9
!%'lO
2
&!%(iO
2
&
D5
!D/
2
O
Mordenite is used ,or hi+h tem$erature (CR o, NO
x
-ith
N/

treatment in dilute acid con#erts this to the /

4
exchan+ed
state

CFi+ure hereE
each line re$resents *O* .onded to (i or 'l at the intersection
(i to 'l ratio is 2 5 and it has 2 non*intersectin+ $ore structures
Main $ore contains 02 oxy+ens in an elli$tical sha$ed a$erture
23!KxK '
o
Minor $ore has 9 oxy+en -ith 22!1 x 5!K '
o
Pro$osed that the ,rame-orB 'lO
*
/
4
or 'lO
*
M
4
,or the acti#e sites ,or
catalytic reactions
(ynthetic )eolites, e!+!, mordenite, +enerally $re$ared ,rom aHueous
solutions o, alBali salts o, aluminium and silicon and sometimes an
or+aninc amine called tem$late, -hich aids in esta.lishin+ a $articular
crystalline structure
Reaction is usually carried out in an autocla#e at tem$eratures .et-een
055 and 095
o
C
!everal Procedures E#ist to Prepare
!upported Catalysts

Lm$re+nation is usually em$loyed in the

industry ,or $ractical %ease& and economic
%chea$& reasons

Lm$re+nation allo-s:

Mse o, $re*sha$ed or structured su$$orts

Mse commercially a#aila.le su$$orts, -hich is

an ad#anta+e since su$$orts -ith o$timal
$ro$erties can .e selected
Precipitation is Another Commonly
$sed %ethod

Lt is essentially a crystalli)ation $rocess that occurs in the

.ulB o, the liHuid or on a relati#ely NinertO su$$ort

Ln .oth methods the $ur$ose is to attach the acti#e $hase

to the su$$ort and to Bee$ the $articles small

For im$re+natin+ se#eral $recursors simultaneously on the

su$$ort it is called co&impre'nation

Lm$re+nation is o, t-o ty$es

8ry im$re+nation %Pust enou+h $recursor solution is used&
Jet im$re+nation %excess Huantity o, $recursor solution is used&
Processes that occur durin'
(mpre'nation

For dry im$re+nation the ,ollo-in+ $rocesses

occur:

"rans$ort o, the $recursor containin+ solution -ithin the

$ore system o, the su$$ort

M$taBe o, the solute %$recursor& .y the $ore -all

For -et im$re+nation the trans$ort o, the solute to

the outer sur,ace is also reHuired

8e$endin+ on the $rocess conditions di,,erent

$ro,iles o, the acti#e $hase o#er the su$$ort is
o.tained
)i#in' of the active phase to the
!upport

The precursor of the active phase are fi#ed to the

support *y
+eaction or e#chan'e with surface O, 'roups
And-Or Adsorption

The O, concentration of the support is crucial

pre&treatment of the support controls O, concentration

)or adsorption the surface char'e plays an important

role
At p, at P"C the surface is neutrally char'ed
At p, . P"C the surface is positively char'ed
At p, / P"C the surface is ne'atively char'ed
p, at P"C depends on support and
pre&treatment

p, at P"C o, some commonly a#aila.le

commercial su$$orts:
'l
2
O

%alumina& 9 to 1
(iO
2
%silica& 2 to
"iO
2
%titania& 5 to 3

$/ at PIC also de$ends on the history %$re*

treatment& and $re$aration method o, the
su$$ort